Synergistic insecticidal composition of diazinon and a certain carbamate

ABSTRACT

INSECTICIDAL COMPOSITIONS WHICH ARE SYNERGISTIC INSECTICIDAL MIXTURES OF O,O-DIETHYL-O-(2-ISOPROPYL-6-METHYLPYRIMIDYL-(4))-THIOPHOSPHATE, KNOWN UNDER THE TRADE NAME OF DIAZINE$ WITH THE CARBAMATE OF THE FORMULA   1-(C2H5-OOC-(CH2)2-),3-CH3,5-((CH3)2-N-COO-)PYRAZOLE   ARE DESCRIBED AS WELL AS METHODS FOR COMBATTING INSECTS USING THESE COMPOSITIONS.

United States Patent 3,755,564 SYNERGISTIC INSECTICIDAL COMPOSITION OFDIAZINON AND A CERTAIN CARBAMATE Kurt Gubler, Riehen, Switzerland,assignor to Ciba-Geigy Corporation, Ardsley, N.Y.

No Drawing. Continuation-impart of application Ser. No. 803,090, Feb.27, 1969. This application Nov. 15, 1971, Ser. No. 199,017

Claims priority, application Switzerland, Mar. 7, 1968, 3,410/68 Int.Cl. A0111 9/22, 9/36 US. Cl. 424-200 4 Claims ABSTRACT OF THE DISCLOSUREInsecticidal compositions which are synergistic insecticidal mixtures of0,0-diethyl-O-(2-isopropyl-6-methylpyrimidyl-(4))-thiophosphate, knownunder the trade name of Diazinon with the carbamate of the formula N -oo Omani):

(BHFCHPCOOCZHE are described as well as methods for combatting insectsusing these compositions.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of patent application Ser. No. 803,090 filed Feb.27, 1969', now abandoned.

DISCLOSURE The present invention concerns insecticidal compositions,which constitute synergistic mixtures of 0,0-diethyl-O-[2-isopropyl 6methyl-pyrimidinyl-(4)]-thiophosphateknown under the name of Diazinon(see British Pat. No. 713,278 or US. Pats. No. 2,754,243, 2,754,244 and2,754,302) with heterocyclic carbamates known from the British Pat.1,031,490 or the US. Pat. 3,342,832 and processes for the controlling ofinsects using the synergistic mixtures.

The term synergistic mixture denotes compositions of two or moreinsecticidally effective compounds, the action of which, in intensity orbreadth, exceeds the sum to be anticipated from the actions of theindividual components. The synergistic action of such a combination,especially in the case of compounds of varying chemical constitution, isnot governed by any rules whatsoever and is not predictable.

It has now been found that mixtures of Diazinon (0,0-diethyl O[2-isopropyl-6-methyl-pyrimidinyl-(4)- thiophosphate) with theheterocyclic carbamate of the formula C 1 CH.

\III/ OCON possess an appreciably higher insecticidal action than can beexpected from the summation of the individual actions. This synergism isshown to a varying degree within a wide range of all possible mixtureratios. The relative amounts of the active substances are not critical.Mixtures may contain Diazinon and carbamate in proportions of 1:1 to :1,

preferred however is the proportion 2:1.

In applying an insecticide, the occurring toxic residues on the crops,which are conveyed to the human or animal food, prevent in many casesthe application of unlimited amounts of active substances. However, alimitation of the applied amount of active substances can lead to areduction of the extent of destruction of the pests, Which even if onlyslight, makes the value of a treatment practically ineffective. Thus forexample, a destruction effect below in the case of the olive fly isinadequate in practice, since the loss of crops is too high and thesurvival level of the pests is suflicient for the formation of anappreciably identical, succeeding generation. It is therefore ofdecisive importance if, by virtue of the addition of a synergist, theeffectiveness of a compound can be increased to the extent that thedesired effect can be achieved with an applied amount, the level ofwhich creates no residue problem, whereas using the individualcomponents to attain the same effect, amounts would be necessary whichwould produce unacceptable residues.

The new synergistic mixtures are particularly suitable for controllingfruit flies on oil fruits. The control of these pests is generallyeffected using phosphorus ester insecticides. Due to the high affinityto the oil fruits, rapid penetration and accumulation in the fruits,there is the possibility of the formation of toxic, undesirable residueswith the application of phosphorus esters in the usual concentrationsrequired for the control of fruit flies. In the new synergisticmixtures, the phosphorus content is considerably reduced, so that theformation of toxic residues is practically eliminated with, at the sametime, an increased insecticidal activity.

The synergistic mixtures, according to the invention, also constitutevery good stomach and contact poisons and exhibit a very good lastingeffect against biting and sucking insects at all stages of development.

Their quick-kill properties should be particularly emphasized, sincespeed of action is an essential property for an insecticide. Thequick-kill properties of the instant synergistic mixtures are clearlysuperior to those of the components of the mixture when used above.

The new synergistic mixtures can for example be used against thefamilies Muscidae, Stomoxidae, Culicidae and Trypetidae such as, e.g.the polyvalent resistant and normally sensitive common house flies(Musca domestica), stable flies (Stomoxys calcitrans) and mosquitoes(e.g. Aedes aegypti, Culex fatigans, Anopheles stephensi), fruit flies,e.g. olive fly (Dacus oleae), Mediterranean fruit fly (Ceratitiscapitata), against the insects of the families Curculionidae,Bruehididae, Dermestidae, Tenebrionidae, Chrysomelidae, Tineidae, e.g.granary weevils (Sitophilus granarius), bean beetles (Bruchidiusobtectus), larder beetles (Dermestes vulpinus), Attagenus and Anthrenus,yellow meal worms (T enebrio molito r), Colorado potato beetles (Leptintarsa decem-lineata), clothes moths (Tineola biselliella), againstinsects of the families Pyralidae, e.g. Mediterranean flour moths,Blattidae, e.g. German cockroaches (Phyllodromia germanica, Periplanetaamericana, Blatta orientalis), against insects of the family Locustidae,e.g. desert locusts (Locusta migratOria), against the familiesNoctuidae, Tortricidae and Yponomeutidae, e.g. Prodenia litura, erminemoth (Ypon'omeuta malinella) etc.

The following tests show the improved insecticidal action of thesynergistic mixtures according to the invention. The individualcomponents are used as comparative active substances. The mixtures wereapplied in the form of aqueous emulsions, which were obtained from a 40%emulsion concentrate of the following composition by diluting withwater:

40 parts of active substance 4 parts of epichlorohydrin 2.5 parts ofisooctylphenyl polyglycolether 2.5 parts of dodecyl benzenesulphonate-calciumv salt 51 parts of xylol.

The following were used as active substances:

(A) 40 parts of Diazinon (B) 40 parts ofl-(p-ethoxycarbonylethyl)-3-methylpyrazolyl-( )-N,N-dimethyl carbamate(C) 26.7 parts of Diazinon and 13.3 parts ofl-[fl-ethoxycarbonylethyl)-3-methylpyrazolyl- (5 -N,N-dimethylcarbamate.

(1) Tests on larva of the olive fly (Dacus oleae) Seven-year-oldRrantoio olive trees (2.3 m. high) with uniformly abundant fruit cropwere treated in clear weather (calm, 24 C.) with aqueous emulsions (produced from the previously mentioned 40% emulsion concentrates), whichcontained g. of insecticide active substance per 100 litres. At thispoint of time, 5% of the fruit had been attacked by the olive fiy(deposit of eggs and larva). 2 trials of each test were madesimultaneously and under the same conditions.

24-26 days after the treatment, 100 olives were picked from each tree(green) with punctures (deposit of eggs by the olive fly), but withoutthe hatching holes of the larva in the pupa stage. The olives were thenexamined with respect to larva alive inside the fruit.

The figures given in the following table are the percentage figures ofmaggot-free (larvae-free) olives and are the average values taken fromthe 3 series of tests.

Percent maggot- Active substance: free olives Diazinon (A) 81.5Carbamate (B) 19.8 Mixture: DiazinonzCarbamate 2:1 (C) 95.7

In this test the synergistic mixture shows a better insecticidalactivity than the individual components. Also worthy of note is thelong-lasting, good effect of the mixture C. It can moreover be shownthat the individual components A and B do not produce the percentagevalue of at least 95% which is required in practice.

(2) Tests with Aedes aegypti Active substance: Time, minutes This testshows that the synergistic mixture destroys mosquitoes in an appreciablyshorter time than the individual components A and B.

(3) Tests on larvae of the cherry fly (Rhagoletis cerasz') Cherry treesof the species coeur de pigeon standing in the Rhone valley near Bex(Switzerland) carrying almost ripe fruits were treated on July 2, 1968with an aqueous spray emulsion (prepared from the previously mentioned40% emulsion concentrate) in such a. manner that for each branch havinga surface of about 2 m 5 l. of spray emulsion were used. The sprayemulsion contained g. of active substance per 100 liter of water. Thetreatment of the cherries occurred at a moment, when the cherry flylarvae of different stades were already inside the fruits. Care wastaken that branches with fruits of similar ripeness were chosen for thetest, i.e. branches which were equally exposed to sunshine. For everytest,

Dead Liv larvae of larvae of difierent dificrent stades stades Activesubstance Concentration 2-7 mm. 2-7 mm.

Diazinon (A) 20 g./100l 37 63 Carbamate (B). 2O g./100 1-. 46 42Mixture: Diazino carbamate 211(0) 20 gJlGUl 161 0 This test indicatesthat the mixture Diazinonzcarbamate 2:1 kills the larvae of the cherryfly inside the fruit more eifectively than the individual components do.

The synergistic mixtures can be used on their own or together with otherpesticidal active substances such as with other insecticides,acaricides, fungicides and nematocides. The amount of synergisticmixture which is to be applied can be varied within Wide limits. Theamount applied depends on the ratio of components, on the type ofpreparation, on the type of insects to be controlled, as well as on thedesired control effect. Depending on the form of preparation, theinsecticidal compositions can have a content of 0.1 to 90 parts byweight of the stated synergistic mixture. In general, the applied concentrations are between 0.05 and 20% relative to the active substancemixture.

All preparation forms normally used for the protection of plants andprovisions can be produced from the synergistic mixtures. This iscarried out in a manner known per se by the intimate mixing and grindingof the active substances with suitable carriers and, optionally, withthe addition of dispersion agents or solvents which are inert to theactive substances.

The following forms of preparation are mentioned:

Solid forms: dusts, sprinkling agents, granulates, such as coatedgranulates, impregnated granules and homogeneous granules.

Water dispersible concentrates of active substances: wettable powders,pastes, emulsions.

Liquid forms: solutions, aerosols.

To produce solid forms (dusts, sprinkling agents, granules), the activesubstances are mixed with carriers. Examples of carriers are, e.g.kaolin, talcum, bole, loess, chalk, limestone, ground limestone,Attaclay, dolomite, diatomaceous earth, precipitated silicic acid,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,milled plastics, fertilisers such as ammonium sulphate, ammoniumphosphate, ammonium nitrate, urea, ground vegetable products, such asbran, bark dust, sawdust, ground nutshells, cellulose powder, residuesof plant extractions, active charcoal etc. Each of these carriers can beused alone or admixed with each other.

The grain size of the carriers is, for dusts, advantageously up to about0.1 mm., for sprinkling agents about 0.075 to 0.2 mm. and for granulates0.2 mm. or more.

As a rule, the concentration of active substance in the solidpreparations is from 0.5 to To these mixtures can also be addedadditives which stabilise the active substance and/or non-ionic, anionicand cationic surface active substances which, for example, improve theadhesion of the active substances on plants and parts thereof (glues,adhesives) and/or ensure a better wettability (wetting agents) anddispersibility (dispersing agents). Examples of such adhesives are asfollows: olein-lime mixture, cellulose derivatives (methyl cellulose),carboxymethyl cellulose), hydroxyethyl glycol ethers of monoand di-alkylphenols having 1-15 ethylene oxide radicals per molecule and 8-9 carbonatoms in the alkyl radical, lignin sulphonic acids, their alkali andalkaline earth metal salts, polyethylene glycol ethers (Carboxwaxes),fatty alcohol polyethylene glycol ethers having -20 ethylene oxideradicals per molecule and 8-18 carbon atoms in the fatty alcohol part,condensation products of ethylene oxide/ propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products ofurea/formaldehyde as well as latex products.

The concentrates of active substance which can be dispersed in water(wettable powders), pastes and emulsion concentrates, are agents whichcan be diluted with water to give any desired concentration. Theyconsist of active substance, carrier, optionally additives whichstabilise the active substance, surface active substances andanti-foaming agents and, optionally, solvents. The concentration ofactive substance in these agents is 580% Wettable powders and pastes areobtained by mixing and grinding the active substances with dispersingagents and pulverulent carriers in suitable devices until homogeneity isattained. Suitable carriers are, for example, those previously mentionedfor solid preparations. It is advantageous in some cases to use mixturesof different carriers. Suitable dispersing agents are, e.g. condensationproducts of sulphonated naphthalene and sulphonated naphthalenederivatives with formaldehyde, condensation products of naphthalene orof naphthalene sulphonic acids with phenol and formaldehyde, alsoalkali, ammonium and alkaline earth metal salts of lignin sulphonicacid, also alkylaryl sulphonates, alkali and alkaline earth metal saltsof dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salt of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyldilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Examples of anti-foaming agents are: silicones, e.g. Antifoam A etc.

The active substances are so mixed, ground, sieved and strained with theabove mentioned additives that the solid particle size in wettablepowders does not exceed 0.02- 0.04 mm. and in the case of pastes 0.003mm. To produce emulsion concentrates and pastes, dispersing agents suchas those statedin the previous sections, organic solvents and water areused. Examples of solvents are: alcohols, benzene, xylenes', toluene,dimethyl sulphoxide and mineral oil fractions boiling between 120 and350 C. The solvents must have practically no smell, be not phytotoxic,inert to the active substances and not easily inflammable.

In addition, the compositions according to the invention can be used inthe form of solutions. For this application, the active substances aredissolved in suitable organic solvents, mixtures of solvents or inwater. Aliphatic and aromatic hydrocarbons, chlorinated derivativesthereof, alkyl naphthalene, on their own or mixed with each other, canbe used as organic solvents. The solvents should contain the activesubstances within a concentration range of 1-20%.

The following forms of compositions according to the invention serve toillustrate the present invention. Where not otherwise expressly stated,the term parts denotes parts by weight.

DUSTS The following substances are used for a 3% dust:

2. parts of Diazinon 1 part of1-(,8-ethoxycarbonyl-ethyl)-3-methyl-pyrazolyl- (S )-N,N-dimethylcarbamate,

0.3 part of epichlorohydrin 96.7 parts of talcum 20 parts of talcum areimpregnated with a mixture of Diazinon and epichlorohydrin andhomogeneously mixed. To this mixture are added the remaining talcumtogether with the carbamate. The mixture is then finely ground in adowelled disc mill. The obtained dust is especially suitable forcontrolling insects in the house, farm, silos and in food storageplaces.

GRANULATE The following substances are used to produce a 6% granulate:

4 parts of Diazinon 2 parts of1-(p-ethoxycarbonyl-ethyl)-3-methyl-pyrazolyl- (5 -N,N-dimethylcarbamate 6 parts of calcium silicate 87.75 parts of ground limestone(grain size 0.4-0.8 mm.)

0.25 part of epichlorohydrin In suitable mixing apparatus, the Diazinonand epichlorohydrin are drawn onto the ground limestone, mixed with 4parts of calcium silicate and subsequently ground with a preliminarymixture of the carbamate and calcium silicate. A granulate is obtainedwhich can be used for ground treatment and anywhere where finelypulyerised material cannot be used on account of the formation of dust.

WETIABLE POWDER The following substances are used to produce a 30%wettable powder:

20 parts of Diazinon 10 parts of 1-(;8-ethoxycarbonyl-ethyl) 3methyl-pyrazolyl-(5)-dimethyl carbamate 35 parts of diatomaceous earth 5parts of magnesium carbonate 20 parts of kaolin 5 parts ofoleyl-methyl-tauride-sodium salt 5 parts of lignin sulphonic acid-sodiumsalt From Diazinon, diatomaceous earth and magnesium carbonate apreliminary mixture is produced, into which the other substances arethen mixed. A wettable powder is thus obtained Which can be diluted withWater to give suspensions of any desired concentration. Thesesuspensions can be used to control biting and sucking insects incultivated plantations such as fruit-free plantations.

SPRAYING AGENT The following substances are used to produce a 4%spraying agent:

3 parts of Diazinon 1 part ofl-(fi-ethoxycarbonyl-ethyl)-3-methyl-pyrazolyl- (5 )-N,N-dimethylcarbamate 10 parts of xylol 86 parts of petroleum This solution isexceptionally suitable for controlling flies and mosquitoes indwellings, warehouses and slaughterhouses.

EMULSION CONCENTRATE The following substances are used to produce a 40%emulsion concentrate;

The active substances are dissolved in the solvent and the stabilisingagent and the emulsifier are then added while stirring, until ahomogeneous solution is attained.

The emulsion concentrates form a finely dispersed milky mixture uponadding to water. After stirring for a short while in order to achieve agood distribution,

8 the emulsion thus obtained can be sprayed onto the plants 3. Thecomposition according to claim 1, also conto be treated. taining acarrier.

What I claim is: v 4. The composition according to claim 2 wherein a 1.An insecticidal, synergistic composition, comprising carrier is alsoincluded.

as active substances insecticidally effective amounts of 0,0-diethyl-O-(2-isopropyl 6 methyl-pyrimidinyl-(4) References Cited thiophosphate andthe carbamate of the formula: UNITED STATES PATENTS CH; 2,754,302 7/1956Gysin et a1 424-200 T] fi 3,342,832 9/1967 Gubler 424-42 -oooNom 10ALBERT T. MEYERS, Primary Examiner CHPCHPC O 0 v. D. TURNER, AssistantExaminer the ratio of phosphate to carbamate being 2:1.

2. The composition according to claim 1, also containing dispersingagent. 424300

